Arylsulfones are important building blocks in organic chemistry and especially in medicinal chemistry. The arylsulfone fragment is found in various drugs, such as the COX-2 inhibitor Vioxx or the prostaglandin D2 antagonist Laropiprant. Diarylsulfones have been shown to exhibit antitumor activities or to inhibit HIV-1 reverse transcriptase.
Because of their importance, numerous procedures for the synthesis of arylsulfones have been reported, such as the oxidation of sulfides, the sulfonylation of arenes, or Pd- and Cu-catalyzed coupling reactions as well as transition-metal-free synthesis of diarylsulfones from arylsulfinic acid sodium salts and diaryliodonium salts.
Article titled, “Arylation of Lithium Sulfinates with Diaryliodonium Salts: A Direct and Versatile Access to Arylsulfones” by Natalie Umierski and Georg Manolikakes in Organic Letters 2013, 15, 188 reports an efficient, transition-metal-free arylation of lithium sulfinates, which are readily accessible from reactions of organolithium reagents with sulfurdioxide. Based on this method, it further reports a practical protocol for the direct transformation of (hetero)arenes and (hetero)aromatic halides into diarylsulfones.
U.S. Pat. No. 3,250,812 discloses a process for producing alkyl aryl sulfones which comprises reacting an aryl compound having free hydrogen on the ring with a compound having the formula (RiSO2)2O, wherein R1 is a lower alkyl radical in a solvent at sufficient temperatures to effect said reaction.
U.S. Pat. No. 4,386,221 disclose a process for the preparation of aryl alkyl sulfones and aryl vinyl sulfones. The process comprises of reacting an aryl compound with an alkyl sulfonyl fluoride or with a vinyl sulfonyl fluoride in the presence of a catalyst selected from AlCl3 and AlBr3.
U.S. Pat. No. 5,015,775 discloses Alkyl aryl sulfones of the formula R—SO3—Ar-Yn, wherein Ar is an aryl compound, Y is a substituent on the aryl compound and R is alkyl or cycloalkyl, and liquid mixtures of positional isomers of the same are prepared by reacting an aryl compound of the formula Ar-Yn, with an alkyl sulfonic acid of the formula R—SO3H and a phosphorus reagent, preferably under heat.
Article titled, “One-step synthesis of α,β-unsaturated arylsulfones by a novel multicomponent reaction of aromatic aldehydes, chloroacetonitrile, benzenesulfinic acid sodium salt” by Lei Zhang, Mao Hua Ding, Hong Yun Guo in Chinese Chemical Letters, Volume 23, Issue 12, December 2012, Pages 1352-1354 reports a new and green method for the synthesis of α,β-unsaturated arylsulfones through the condensation of aromatic aldehydes, chloroacetonitrile, benzenesulfinic acid sodium salt in the presence of 1-butyl-3-methyl imidazolium hydroxide ([bmim]OH) in EtOH under reflux. The ionic liquid was recovered and recycled for subsequent reactions. The advantages of this protocol were non-toxic, easy work-up and good yields.
Article titled, “A mild and efficient new synthesis of aryl sulfones from boronic acids and sulfinic acid salts” by Christian Beaulieu, Daniel Guay, Zhaoyin Wang and David A. Evans in Tetrahedron Letters 45 (2004) 3233-3236 reports a new efficient and mild preparation of sulfones from boronic acids and sulfinic acid salts. The cross-coupling reaction mediated by cupric acetate gives access to a variety of sulfones in excellent yield.
Article titled, “Synthesis of Aryl Sulfones via 1-Proline-Promoted CuI-Catalyzed Coupling Reaction of Aryl Halides with Sulfinic Acid Salts” by Wei Zhu and Dawei Ma in J. Org. Chem., 2005, 70 (7), pp 2696-2700 reports The CuI/I-proline sodium salt catalyzed coupling reaction of aryl halides with sulfinic acid salts readily occurs at 80-95° C. in DMSO to give the corresponding aryl sulfones in good to excellent yields. This process is well-tolerated by a wide range of functional groups including hydroxyl, amino, acetanilide, ketone, ester, and nitrile. Using this method, 4-phenylsulfonyl- and 4-methanesulfonyl-substituted 1-phenylalanine derivatives are prepared.
U.S. Pat. No. 5,468,903 relates to a process for preparing a compound comprising a monocyclic aromatic ring having at least a first substituent and a substituted sulphonyl group at the position para to the first substituent, the process comprising mixing a reactant comprising the monocyclic aromatic ring with the first substituent and hydrogen in the position of the ring para to the first substituent, with a sulphonic acid halide derivative in the presence of a naturally occurring or synthetic zeolite capable of catalyzing a sulphonylation reaction between the reactant and the sulphonic acid halide.
U.S. Pat. No. 6,455,738 B1 relates to a process for the sulfonation of an aromatic compound, said process comprising the steps of:                a) reacting said aromatic compound with a sulfonating agent, in the presence of a catalytically effective amount of a catalyst which is a mixture of bismuth trihalide and of perfluoroalkanesulfonic acid, with a molar ratio less than the stoichiometry resulting in the complete exchange of the halide by the sulfonic functional group, to obtain a sulfonated aromatic compound, and        b) recovering the sulfonated aromatic compound obtained in step (a).        
U.S. Pat. No. 4,950,793 discloses a process of reacting an aromatic hydrocarbon with a halogenated sulfonic acid in the presence of a Lewis acid to obtain an aromatic sulfone compound.
U.S. Pat. No. 5,276,196 relates to the synthesis of bis(haloarylsulfonyl) aromatic compounds and more specifically, bis(chlorophenylsulfonyl) aromatic compounds. A process has been reported wherein product of high purity and minimal iron contamination is produced by reacting haloarylsulfonyl halide with an aromatic compound in the presence of an appropriate catalyst with and without solvent.
U.S. Pat. No. 2,743,290 relates to a process for the production of halogenated thioesters of a sulfonic acid.
However, till date arynes have not been used for such transformation.